DE2712866A1 - PROCESS FOR PRODUCING SULFUR-CONTAINING ORGANOSILICIUM COMPOUNDS - Google Patents

Description

2712856

GERMAN GOLD AND SILVER SCHEIDEANSTALT FORMERLY ROESSLER Frankfurt am Main, Weissfrauenstrasse 9

Process for the preparation of organosilicon compounds containing sulfur

The invention relates to a new process for the production of sulfur-containing organosilicon compounds, which is carried out in a simple, safe and problem-free manner from readily available starting materials, without the formation of harmful by-products and with a practically quantitative course of the reaction.

A process is known for producing bis (alkoxysilylalkyl) oligosulfides from the corresponding alkoxysilylalkyl halides by reaction with alkali metal oligosulfides, preferably in alcoholic solution (BE-PS 787 6 ^Q 1). The alkoxysilylalkyl halides, in turn, are obtained from the halosilylalkyl halides in a customary manner by alcoholysis.

A process has also been proposed for preparing bis (alkoxysilylalkyl) oligosulfides from halosilylalkyl halides by reacting with alcohol, alkali metal hydrogen sulfides and sulfur in a so-called one-pot reaction, hydrogen sulfide being produced as a by-product, so that a portion, one mole, of the sulfur used is not utilized when it is not incorporated into the molecule of the oligosulfide. In practice, the hydrogen sulphide cannot be recovered, but it cannot be released into the atmosphere either.

To eliminate this disadvantage and to proceed as quantitatively as possible Process without the creation of toxic or environmentally hazardous substances Finding by-products was the object of the invention. The process found for the preparation of sulfur-containing organosilicon compounds the formula

(I) Z - Alk - S _x - Alk - Z

in the Z for the groupings

-Z-

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27 1 23oB

R ¹ R ¹ R ²

-Si R ¹ , -Si R ² , -Si- R ² or -Si (OCHR ³ CHR *) ₃ N

R ² R ² R ²

in which R ^{1 is} an alkyl group with a straight or branched chain of 1 to 5 carbon atoms, a cycloalkyl group with 5 to 8 carbon atoms, the benzyl group or the phenyl ^{group optionally substituted by methyl, ethyl or chlorine, R 2 is} an alkoxy group with a straight or branched carbon chain with one to k carbon atoms, the methoxyethoxy group, a cycloalkoxy group with 5 to 8 carbon atoms, the phenoxy group or the benzyloxy group, where R ¹ and R ^{2 can} each have the same or different meanings, R ³ and R *, identical or different, Methyl, ethyl, n-propyl or i-propyl, alk a divalent saturated hydrocarbon radical with 1 to 5 carbon atoms with a straight or branched carbon chain, which is optionally interrupted by -0- », -S- or -NH-, and χ a Number from 2.0 to 6.0, characterized in that an alkali metal alcoholate in preferably alcoholic solution with a conn using the formula

(II) Z - Alk - Shark,

in which Z has the meanings given above and Hai is a chlorine, Brom- or Jodatora, with a hydrogen sulfide of the formula

(ill) MeSH,

in which Me is ammonium, an alkali metal or an equivalent of an alkaline earth metal atom or the zinc, and with sulfur preferably reacted in the presence of at least one organic solvent, separated from the halide formed and given If the organic solvent is removed.

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The starting materials II, so the Halogenalkyloxysilane are prepared by processes known per se as shown by hydrosilylation of simple, unsaturated halogenated hydrocarbons, for example, by the addition of trichlorosilane to allyl chloride in the presence of noble metal catalysts with subsequent alcoholysis of the Trichlorsilylpropylchlorids wherein generalizes

^ Si-HaI bond in the molecule is converted into a ^ Si-OR bond . Has such a halosilane three -OR groups, it may also according to known procedures using transesterification with triethanolamine or an alkyl-substituted on carbon triethanolamine converted to a Halogenalkylsilatran.

In general formula II, Hal denotes a halogen atom, in particular chlorine, bromine or iodine, preferably chlorine. Halosilanes of the formula II are, for example Chlormethyldimethoxysilan, 2-Chloräth.ylcliäthoxyäthylsilan, 2-Brornäthyl tri-i-propoxysilane, 2-Chloräthyltriäthoxysilan, 3-chloropropyltrimethoxysilane, J- ChIorpropyldiäthoxymethylsilan, 3-Chlorpropylcyclohexoxydimethylsilan, ^ -Brombutyldiäthoxybenzylsilan, 4-Jodbutyltrimethoxysilan, 5- Chio rpentyldimethoxyphenylsilane, 3-bromo-i-butyltriäthoxysilane, 3-chloropropyl-p-chlorophenylsilane, 2-chloro-i-propyl-ethoxy-p-ethyIphenylsilan, 3-chloropropylethoxymethylethylsilane, 3-chloropropyl-p-chlorophenylsilane, 5-iodine-nano Brompropyldimethoxycyclopentoxysilan, 2-chloro-2 '-methyläthyldiäthoxycycloheptoxysilan, 3-bromo-2 * -methyl-propyldimethoxycyclooctylsilan, 3-Chlorpropyldiäthoxy-2'-raethoxy-ethoxy silane, 2-Chloräthyldimethylcyclooctyloxysilan, 3-Chlorpropyldibutoxymethylsilan, 3-Brompropylphenyloxydimethoxysilan, 3-Chlorpropyldi- i-butoxy-2'-methylphenylsilane and 3-chloro-3'-methylpropyl-dimethoxybenzyloxysilane.

The alkali metal component of the alcoholate is in particular potassium and preferably sodium, while the alcoholic component is preferably an aliphatic, primary alcohol such as methyl alcohol, Is ethyl alcohol, propyl alcohol, i-propyl alcohol, uutyl alcohol, etc., It is advisable to use freshly prepared alcoholate with excess Alcohol used, this being alcohol or a mixture

809839/0401

-> - 2 7 1 2 Γ * S β

of alcohols at the same time serves as a solvent for the reaction. The alcohol or part thereof can advantageously be used here already come from the alcohol of the previous alcoholysis mentioned above.

In the general formula III, Me means in particular the ammonium radical, Sodium, potassium, an equivalent of the metals magnesium, calcium, strontium, barium or zinc. When performing the inventive Process are preferably sodium, potassium, calcium or ammonium hydrogen sulfide as compounds of the formula III used. They are preferably used in as finely divided a form as possible, for example in powder form.

In the formulas I and II, Alk denotes methylene and, preferably, ethylene, i-propylene, N-propylene, i-butylene or n-butylene but also n-pentylene, 2-methylbutylene, 3-methylbutylene, n-pentylene, Mean 1,3-dimethylpropylene and 2,3-dimethylpropylene. Alk can also have the following meanings:

-CH ₂ -S-CH ₂ -; -CH ₂ -O-CH ₂ -; -CH ₂ -NH-CH ₂ -; -CH ₂ -S-CH ₂ CH ₂ -; -CH ₂ -O-CH ₂ CH ₂ -; -CH ₂ -NH-CH ₂ CH ₂ -; -CH ₂ CH ₂ -S-CH ₂ CH ₂ -; -CH ₂ CH ₂ -O-CH ₂ CH ₂ -; -CH ₂ CH ₂ -NH-CH ₂ CH ₂ -; -CH ₂ -S-CH ₂ -S-CH ₂ -; -CH ₂ -0-CH ₂ -0-CH ₂ -; -CH ₂ -NH-CH ₂ -NH-CH ₂ -; -CH ₂ -S-CH ₂ CH ₂ -S-CH ₂ -; -CH ₂ -0-CH ₂ CH ₂ -0-CH ₂ -; -CH ₂ -NH-CH ₂ CH ₂ -N 1 _{-CH 2} -; -CH ₂ CH ₂ -S-CH ₂ -S-CH ₂ CH ₂ -; -CH ₂ CH ₂ -0-CH ₂ -O-CH ₂ CH ₂ -; -CH ₂ CH ₂ -NH-CH ₂ -NH-CH ₂ Ch ₂ -;

To carry out the reaction according to the invention, the elementary Sulfur advantageously used in finely divided form, for Example as commercially available sulfur powder. Also the hydrogen sulfide is preferred to accelerate the reaction process also used in powder form. The reaction generally starts at room temperature after the reactants have been brought together, and it can proceed as an exothermic reaction by itself. Appropriately, for Shortening the total reaction time with increased or increasing

-5-

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Temperature worked, which up to the boiling point of the used Solvent or solvent mixture can be increased. The use of an inert organic is particularly advantageous Solvent or solvent mixture with a boiling point that is not too high, which completely affects the reactants used or is able to solve in part. Such solvents are, for example, dioxane, dimethylformamide, tetrahydrofuran and in particular Acetone and preferably alcohols, primarily primary low-aliphatic or cycloaliphatic alcohols, and optionally their mixtures.

Furthermore, it is advantageous to carry out the reaction with the exclusion of air and / or water (moisture) in order to achieve the formation of by-products to be suppressed or largely avoided. One can, for example, under dry inert gas such as nitrogen or work under one of the noble gases. It can also be advantageous to carry out the reaction under reduced pressure; easy increased pressure is also not excluded.

In the new reaction, in contrast to the previously proposed reaction mentioned at the outset, with only one hydrogen sulfide and sulfur is no hydrogen sulfide, which is used to To avoid environmental pollution, it must be burned catalytically if it is not reused in the cycle or otherwise required will. During the reaction, only the alkali metal halide and alcohol are produced, which are recovered together with the solvent alcohol will. The course of the reaction is practically quantitative according to the following equation:

-Si-Alk-Hal + MeOR + MeSH +

Si ^ + 2 MeHaI + RAW.

This equation also gives the molar quantities to be used Compounds and sulfur. The exothermic reaction generally occurs even at moderate temperatures 20 to 80 ° C. in progress in is expediently ended towards the end of the reaction at the reflux temperature. A certain

809839 / (KQI

271236b -g-

Post-reaction time can be an advantage. After the reaction has ended, the reaction mixture is cooled to remove the salt that has separated out filtered off and then the organic solvent or solvent mixture is advantageously removed by distillation, expediently under reduced pressure. The sulfur-containing organosilicon compounds formed as end products can be obtained from conventional Conditions cannot be distilled without decomposition. In practice, they are collected in the distillation sump and can in most cases can be put directly to the desired use without cleaning. For example, they can be considered valuable Adhesion promoters or reinforcing additives in silicate fillers containing rubber mixtures are used. But they also represent valuable intermediate products.

The poly- or oligosulfidic silanes according to the general formula I are for the most part known (BE-PS 787 61-1), but they are accordingly produced by other processes. It is also already known that these silanes can be prepared by direct reaction of mercaptoalkylsilanes with sulfur (DT-OS 2h 05 758). DT-OS 23 6o ^ 71 also describes a process in which the incorporation of elemental sulfur into organosilylalkyl disulfides corresponding polysulfides are obtained. However, this known method has some serious disadvantages compared to the method according to the invention. While the process according to the invention is based on the readily available haloalkylsilanes and the polysulphides are obtained in one reaction stage, in the known process, the mercaptoalkylsilanes must first be converted from these haloalkylsilanes and, from this, the disulphides required as starting compounds for that process as starting compounds through oxidation, i.e. through a further reaction step getting produced. That is a total of three reactions. Furthermore, reaction times in the known process of 15 to 50 hours at reaction temperatures of around 150 ° C. represent a further important disadvantage. Compared to all known syntheses, the process according to the invention is surprisingly simple. The equipment and the time required to carry out the new Verl'alirens are low and the process of

809839/0401

Ileaction is practically quantitative. The new process is technically and economically clearly superior to all previously known processes with readily available starting materials.

Preferred silanes according to the formula I are the bis- / trialkoxysilyl-alkyl- (l) / - polysulfides such as the dis- / trimethoxy-, -triethoxy-, -tri- (methylethoxy) -, - tripropoxy-, -tri-i- propoxyu.-sf up to the -tripentoxysilyl-methylZ-polysulphides, furthermore the I3is- / 2-trimethoxy-, -triethoxy-, - tri- (methylethoxy) -, -tripropoxy-, -tri-i-propoxy- etc. up to the tripentoxysilyl-ethyl _y ⁷ -polysulfides, specifically the di-, tri-, tetra-, perita- and ilexasulfides, especially the bis- / 3-trimethoxy-, -triethoxy -, - tri- (methylethoxy) -, - tripropoxy-, -tri-i-propoxy-, -tributoxy- etc. up to the -tripenoxypropyl / -polysulfiden and indeed again the di-, tri-, tetra etc. up to the hexasulfides, furthermore the corresponding bis- ^ 3-trialkoxysilyl- -isobutyl / -polysulfide, the corresponding His- / li-trialkoxysilylbutyl / -polysulfide etc. up to the bis- / 5-trialkoxysilylpentylZ-polysulfides. Of these selected, relatively simply structured organosilanes of the general formula I, the bis- / 3-trimethoxy-, -triethoxy- and -tri-propoxysilyl-propyl_ / - polysulfides, preferably the tri-, tetra- and peiitasulfides, are again preferred . Examples of silanes according to the formula I prepared according to the invention are further specifically: bis- (3-trinethoxysilylpropyl) -trisulfide, bis- (3-triethoxyilylpropyl) -tetrasulfide, bis- (3-trimethoxysilylpropyl) -tetrasulfide, bis- ( 2-triuthoxysilylethyl) -tetrasulfide, bis- (3-trimethoxysilylpropyl) -disulfide, bis- (3-triäthoxysilylpropyL) -trisulfid, bis- (3-tributoxysilylpropyl) -pentasulfid, ßis- (3-trii.mthoxysilylpropyl) -trisulfid , Bis- (3-trioctoxysilylpropyl) -tetrasulfide, bis- (3-trihexoxysiJ ylpropyl) -pentasulfide, bis- / 3-tris- (2'-ethylhexoxy-si IyIpTOj) yl / -tctrasulfid, bis-tri (3 -ist) oc toxys i lylpropyl) -tetrasulphide, bis- (tris-1-but oxy si IyI nie thyl) -trisulphide, bis- (2-methoxydiäthoxysilyläthyl) - te tr: i sulphide, bis- (2- t ri -i-propoxysi 1 yläthyl) -pontcisulfid, Bis- (3- tricyclohexoxysilyl jjropyl) -tetrasulfid, Bis-

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2712S56

(3-tricyclopentoxysilylpropyl) -trisulfide, bis- / 3-tris- ('' »'-methylcyclohexoxysilyliithyl / -tetrasulfide , Bis- (dime thoxyphenoxy Si Iy Im ethyl) -tetrnsulfid, bis- (3- <liinethoxymethylsilylpropyl) -di, -tri- and tetrasulfide, bis- (3-di'ethoxyäthylsilylpropyl) -di, -tri- and -tetrasulfide, bis- (3-diethoxymethylsilylpropyl) -di, -tri- and -tetrasulfide, bis- (3-diethoxyäthylsilylpropyl) -di, -tri- and -tetrasulfide, bis- (3-methoxydimethylsilylpropyl) -di, -tri- and -tetrasulfide, bis- (3-üthoxydiniethylsilylpropyl) -di, - tri-tetrasulfide, bis- (3-tliäthyläthoxysilylpropyl) -tetrasulfid, Bis (2-dimethoxymethylsilylethyl ) -disulfide, bis- (3-di-i-propoxyinethylsilyl propyl) -di, -tri- and -tetrasulfide, bis- (3-di-i-propoxyäthylsilylpropyl) -di, -tri- and -tetrasulfide, bis- ('»-diäthoxyüthylsilylbutyl) trisulfid, Bis (5-triethoxysilylpentyl) pentasulphide, bis (5-phenyldimethoxysilylpentyl) tetrasulphide, Bis (4-triethoxysilylbutyl) -hexasulfid, Bis-Z ^ -äthyl-bis- (methoxyethoxy) -silyl-butyl / -tetrasulfide, 3-methoxyethoxypropoxysilylpropy1-3'-dimethoxyüthoxysiIyIyIpropyltetrasulfid, Bi s- (3-methy1-dimethoxysiIyIpropyl) -pentasulfid, Bis (2-dimethoxyphenylsilylethyl) trisulfide, bis ( 3- '"e thy lbu ty läth oxysi IyI propyl) - tetrasulfide, bis- (2-ethyl diethoxysiIyI-i-propyl) -tetrnsulfid, Bis- (3-silatranopropyl) -di, -tri- and -tetrasulfide, bis- (2-silatranoiithyl) -di, -tri- and -tetrasulfide, bis- (2-silntrano-i-propyl) -di, -tri- and -tetrasulfide as well as bis- (3-silatrano-i-butyl) -di, -tri- and -tetrasulfide.

809839/040 1

_ / \ Λ ■

One that can be produced, for example, by the method according to the invention Silatran is the bis-1, 1θ (bicyclo / 3, 3, 3 / -l-aza-5-sila-4, 6,11 trioxa-undecyl) -4,5-6,7-tetrathiadecane of the formula

CH ₂ CII ₂ O OCH ₂ CH ₂ N CH ₂ CH ₂ O Si - (CH ₂ ) ₃ -S "- (CH ₂ ) ₃ -Si- OCH ₂ CH ₂ -N QI ₂ CH ₂ O 'OCH ₂ CH ₂ ' Examples

In a two liter three-necked flask equipped with a stirrer, internal thermometer, reflux condenser and solids filling device, 11.5 g of sodium (0.5 mol) were dissolved with evolution of hydrogen after initially introducing 500 ml of ethanol. After the reaction had ended, 24o.5 g (1.0 mol) of 3-chloropropyltriethoxysilane were then added at 45.degree. Thereafter were 23iO g NaSH (0.5 moles) and finally 48, O g of sulfur powder (1.5 mol) was added and then heated to red-colored reaction mixture to 70 ⁰ C. In an exothermic reaction, the color changed to yellow-gray. After heating to the reflux temperature of about 80 ° C. for one and a half hours, the mixture was cooled, the sodium chloride formed was filtered off and the excess ethyl alcohol was distilled off from the filtrate under reduced pressure.

What remained was the light yellow bis (3-triethoxysilylpropyl) tetrasulfide in an amount of 255.0 g, that's 95 »2'ό of theory. The named compound was identified by NMR and IR spectra and elemental analysis. The latter analysis revealed the following values:

C H Si S

calculated: 4o, ll 7.84 10.42 23.79 found: 38.20 7.43 9.82 23.46

The refractive index n * ¹ was measured to be 1.4937.

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2. to 10. In the same way as described in Example 1, were other organosilanes, the starting substances and analyzes of which are summarized in Table 1 below, manufactured.

- 11 -

809839/0401

Table 1

At- I apielj

Auagangaau dance Established connection Alcohol ■ Katriun

Silane U)

NaSH I S

(e) U)

formula

Elemental analyzes in weight -Jb upper value: calculated lower value: found

Si

C ₂ H ₅ OH!

j 11.5

Cl (CH ₂ Jj

240.8

23.0; 32.0 I.

/ (CjH, 0) jSi (CH ₂ ), 7 ₂ Sj

42.65; 8:35 08.11, 18.98 40. 9h · 'j 8:04 10.64 18:22

ί! ι '

! C ₂ H) OH ι! 500

11.5

Cl (CHj), Si (OC ₂ H ₅ ), 8/24

23.0 16.0

/ TC ₂ H ₅ O), Si (CHj) ₃ Z ₂ S ₂

45.53 j 8.92 ■■ 11.83! 13.51 '»4.17 8.64 ι 11.48 I 13.10

ι. ί CHjOH ί 500

11.5

Cl (CH ₂ ) j Si (OCHj) ₃ 198.8

48.0

/ (CH, 0), Si (CH ₂ ), / ₂ S »

31.69 6.65 j 12.35 I 28.20 j 30.42 6.38 11.88! 27.51 I.

ι! ι

CH ₃ OH 500

11.5

Cl (CH ₂ ) ₃ Si (OCH ₃ ), 198.8

23.0 32nd

/ (CH, O) ₃ Si (CH ₂ ), 7 _a S,

34.09 and 7.15 33.07 I 6.93

13.29 ί 22.75 IX 12.89 22.09; «Yy *

CH, OH 500

11.5

Cl (CH ₂ ) j Si (OCH,), 198.8

23.0 16.0

/ (CH, 0), Si (CH ₂ ), 7 ₂ S ₂

36.89 j 7.74
35.42 7.43

14.38 ί 16.42 '13.85! 15.78 i

C ₂ H ₅ OH 500

11.5

C1 (CH ₂ ) ₂ Si (OC ₂ H ₅ ), 226.8

23.0! 48.0

/ (c ₂ H ₅ 0), Si (CH ₂ ) ₂ 7 ₂ S »

37.62 i 7.50 36.49 7.28

11.00 IO.63

25.10 24.39

C ₂ Hj OH 500

11.5

Cl (CH ₂ ) ₂ Si (OCjH ₅ ), 226.8

23.Ο 32.Ο

/ (C ₂ H ₅ O) ₃ Si (CHj) j7j S, 40.13

39.33

8.00 7.82

11.73 20.09 11.50 19.66

CH ₃ OH 500

11.5

Cl (CH ₂ ), Si (OCH ₃ ), 184.7

23.θ! 48.0

/ (CH ₃ O) ₃ Si (CH ₂ ) ₂ 7 ₂ S _%

28.15; 6.14
March 27, 5.91

13.16 12.64

05/30

29.15

CH ₃ OH II Cl (CH ₈ ) j Si (OCH ₃ ),

11.5 184.7

32nd

) ₂ 7 _a s ₃

30.43 29.27

6.64 6.37

14.23 24.37 13.68 23.40

Claims (3)

Claims 1 ,: 'Process for the production of sulfur-containing organosilicon compounds the formula (I) Z - Alk - S _x - Alk - Z
in the Z for the groupings R ¹ R ¹ R ² -Si R ¹ , -Si ^{-R 2} , -Si R ² or -Si (OCHIi ³ CHR *) ₃ N R ² R ² R ² in which R ^{1 is} an alkyl group with a straight or branched chain with 1 to 5 carbon atoms, a cycloalkyl group with 5 to 8 carbon atoms, the benzyl group or the phenyl ^{group optionally substituted by methyl, ethyl or chlorine, R 2 is} an alkoxy group with a straight or branched carbon chain with 1 to h carbon atoms, the methoxyethoxy group, a cycloalkoxy group with 5 to 8 carbon atoms, the
Phenoxy group or the benzyloxy group, where R ¹ and R ^{2 can} each have the same or different meanings, R ⁵ and R *, identical or different, methyl, ethyl,
n-propyl or i-propyl, Alk is a divalent saturated one
Hydrocarbon radical with 1 to 5 carbon atoms with a straight or branched carbon chain, optionally through
-0-, -S- or -NH- is interrupted, and χ is a number from 2.0 to 6.0, characterized in that an alkali metal alcoholate in preferably alcoholic solution with
a compound of the formula (II) Z- Alk - Shark, in the Z has the meanings given and Hai is a chlorine,
Is bromine or iodine atom, with a hydrogen sulfide 809839 / CU01 ORIGINAL INSPECTED 2712 formula (ill) MeSH, in which Me is ammonium, an alkali metal atom or an equivalent of an alkaline earth metal atom or the zinc, and reacts with sulfur, preferably in the presence of at least one organic solvent, separates it from the halide formed and, if necessary, removes the organic solvent. 2. The method according to claim 1, characterized in that the reaction with a hydrogen sulfide from the series sodium, Potassium, calcium or ammonium hydrogen sulfide in powder form and powdered sulfur. 3. Process according to Claims 1 and 2, characterized in that the reaction is carried out in alcoholic solution at temperatures from 20 ° C to the boiling point of the alcohol or alcohol mixture. PAT / Gt-Pr
March 23, 1977 809839/0401